CN114024057A - Method for recycling waste nickel cobalt lithium manganate-lithium titanate battery - Google Patents
Method for recycling waste nickel cobalt lithium manganate-lithium titanate battery Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
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- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The scheme provides a recovery method of waste nickel cobalt lithium manganate-lithium titanate batteries, and the scheme separates and collects electrolyte in the waste batteries in a low-temperature heating mode in a closed device, so that battery diaphragms cannot be decomposed under a low-temperature heating condition, the recovery and utilization of subsequent diaphragms are facilitated, and meanwhile, toxic and harmful gases such as a large amount of chlorides and dioxin are prevented from being generated by high-temperature heating. The scheme adopts a roasting method, only a small amount of acid is needed to leach the nickel, cobalt, manganese, lithium and titanium, and unnecessary metal copper, iron and aluminum are left in waste residues, so that the workload and the raw material consumption of subsequent iron, aluminum and copper impurities are reduced, and the amount of the waste residues is reduced. In addition, by adopting the recovery method, the separation rate of titanium and nickel, cobalt, manganese and lithium is high, and the recovery rate of titanium, nickel, cobalt, manganese and lithium can reach 98.2 percent.
Description
Technical Field
The invention relates to the field of lithium battery recovery, in particular to a method for recovering waste nickel cobalt lithium manganate-lithium titanate batteries.
Background
The lithium nickel cobalt manganese oxide-lithium titanate battery has the advantages of long cycle life, high safety, wide use temperature range, good rate capability and the like, and is particularly concerned by the industry in recent two years. With the rapid development of new energy industry, a large number of nickel cobalt lithium manganate-lithium titanate batteries face the problem of scrapping treatment in the future. Untreated chemical substances such as battery anode and cathode materials and polyolefin diaphragms cause serious pollution to the ecological environment, so that the development of an efficient recovery method of nickel cobalt lithium manganate-lithium titanate is beneficial to environmental protection and can avoid resource waste.
The nickel cobalt lithium manganate-lithium titanate battery mainly comprises four parts, namely a positive electrode, a negative electrode, an electrolyte and a diaphragm, and at present, the recovery process of the nickel cobalt lithium manganate-lithium titanate battery usually needs to disassemble and crush the nickel cobalt lithium manganate-lithium titanate battery, and then obtain valuable metals such as lithium, cobalt, nickel, manganese and the like through processes of leaching, extraction, precipitation and the like by using a chemical solvent. In the prior art, the battery liquid and the diaphragm are mainly separated in a high-temperature heating mode in a disassembling link, and a large amount of flue gas containing harmful components such as chloride, dioxin and the like is generated in the heating process, so that secondary pollution is generated to the environment.
In addition, in the prior art, strong acid and hydrogen peroxide are generally adopted to dissolve the anode battery powder of the waste battery, copper, iron and aluminum in the battery powder enter the solution at the same time, a large amount of waste residues are generated in the subsequent impurity removal step, and the consumption of acid and alkali is huge, so that the resource waste and the recovery cost are increased. In addition, the separation rate of titanium, nickel, cobalt, manganese and lithium and the recovery rate of nickel, cobalt and manganese are not ideal in the prior art.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for recovering waste nickel cobalt lithium manganate-lithium titanate batteries, which comprises the following steps:
step 1: crushing the pretreated waste nickel cobalt lithium manganate-lithium titanate battery to obtain a crushed material;
step 2: placing the crushed materials in a closed environment for heating reaction, and collecting condensed electrolyte through negative pressure to obtain solid materials, wherein the reaction temperature is 100-250 ℃;
and step 3: carrying out physical separation on the solid material to obtain copper, iron, aluminum, a diaphragm and battery powder;
and 4, step 4: adding an additive A and an additive B into the battery powder obtained after physical separation, uniformly mixing, and roasting in a nitrogen protective atmosphere, wherein the additive A is one or two of sodium sulfate and sodium chloride, and the additive B is one or two of simple substance carbon and simple substance sulfur;
and 5: adding the roasted battery powder into water, continuously stirring under the protection of nitrogen, slowly adding 98% concentrated sulfuric acid, and adjusting the pH value of the solution to be 0.5-2.5, wherein the mass ratio of the battery powder to the water is 1: 2.5-10;
step 6: filtering under nitrogen protection atmosphere, introducing air or oxygen into the filtered solution, stirring for 2-10 hr, and filtering to obtain H2TiO3Precipitating and dissolving nickel, cobalt, manganese and lithium sulfate;
and 7: adding water and an impurity removing agent into the nickel-cobalt-manganese-lithium sulfate solution, adjusting the pH value of the nickel-cobalt-manganese-lithium sulfate solution to 3.5-5.0, and filtering to obtain the nickel-cobalt-manganese-lithium sulfate solution with impurities removed;
and 8: adding an ion concentration regulator into the nickel-cobalt-manganese-lithium sulfate solution after the impurities are removed to enable the molar ratio of nickel, cobalt and manganese in the nickel-cobalt-manganese-lithium sulfate solution after the impurities are removed to be one of 1:1:1, 5:2:3, 6:2:2 or 8:1:1, then adding a sodium hydroxide solution, filtering, washing and drying to obtain a nickel-cobalt-manganese three-element composite hydroxide, filtering to obtain a lithium solution, and performing sodium carbonate precipitation, filtering, washing and drying to obtain lithium carbonate.
Preferably, the step 3 further comprises the following steps:
carrying out secondary crushing on the solid material, wherein the diameter of the material after secondary crushing is less than 1.5 cm;
and screening the materials subjected to secondary crushing, and then carrying out magnetic separation and gravity separation to obtain copper, iron, aluminum, a diaphragm and battery powder.
Preferably, the heating temperature in the step 2 is 150-200 ℃.
Preferably, the impurity removing agent is one or more of sodium hydroxide, sodium carbonate, nickel hydroxide, nickel carbonate, cobalt hydroxide, cobalt carbonate, manganese hydroxide, manganese carbonate, lithium hydroxide, lithium carbonate, sodium sulfide, nickel sulfide, cobalt sulfide, manganese sulfide and lithium sulfide.
Preferably, the ion concentration regulator is one or more of nickel sulfate, nickel chloride, cobalt sulfate, cobalt chloride, manganese sulfate and manganese chloride.
Preferably, the ion concentration range in the nickel, cobalt, manganese and lithium sulfate solution after impurity removal in the step 7 meets the following requirements: ni + Co + Mn + Li is more than or equal to 60g/L and less than or equal to 160g/L, and the mass ratio of ions meets the following requirements: (Ni + Co + Mn + Li)/(Cu + Fe + Al + Ca + Mg) is not less than 3300.
Preferably, the molar ratio of lithium in the battery powder to sodium in the additive A in the step 4 is 1: 1-10, and the molar ratio of lithium in the battery powder to the additive B is 1: 1-3.5.
Preferably, in the step 3, the copper content of the battery powder is 0.2-6.0%, the aluminum content is 0.2-6.0%, and the iron content is 0.2-6.0%.
The beneficial effect of this application is as follows:
1. in the sealing equipment, the electrolyte in the waste battery is separated and collected by adopting a low-temperature heating mode, the battery diaphragm cannot be decomposed under the low-temperature heating condition, the recycling of the subsequent diaphragm is facilitated, and meanwhile, the generation of a large amount of toxic and harmful gases such as chloride, dioxin and the like by high-temperature heating is avoided.
2. According to the scheme, the roasting method is adopted, nickel, cobalt, manganese, lithium and titanium can be leached out only by using a small amount of acid in the follow-up process, unnecessary metal copper, iron and aluminum are left in waste residues, the workload and the raw material consumption of follow-up iron, aluminum and copper impurities are reduced, and the amount of the residues is reduced.
3. The separation rate of titanium and nickel-cobalt-manganese-lithium is high, and the recovery rate of titanium, nickel, cobalt, manganese and lithium can reach 98.2%.
Drawings
For a clearer explanation of the embodiments or technical solutions in the prior art of the present invention, the drawings used in the description of the embodiments or prior art will be briefly described below, and it is obvious for those skilled in the art that other drawings can be obtained based on these drawings without creative efforts.
Fig. 1 is a flowchart of a method for recovering waste lithium nickel cobalt manganese oxide-lithium titanate batteries according to an embodiment of the present invention.
Detailed Description
In order to make those skilled in the art better understand the technical solutions in the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making creative efforts based on the embodiments of the present invention, shall fall within the protection scope of the present invention.
Aiming at the existing defects, the scheme provides a method for recycling waste nickel cobalt lithium manganate-lithium titanate batteries. Referring to fig. 1, a flow chart of a method for recycling waste lithium nickel cobalt manganese oxide-lithium titanate batteries according to an embodiment of the present invention is shown. The method comprises the following specific steps:
s100: crushing the pretreated waste nickel cobalt lithium manganate-lithium titanate battery to obtain a crushed material;
s200: placing the crushed materials in a closed environment for heating reaction, and collecting condensed electrolyte through negative pressure to obtain solid materials, wherein the reaction temperature is 100-250 ℃;
s300: carrying out physical separation on the solid material to obtain copper, iron, aluminum, a diaphragm and battery powder;
s400: adding an additive A and an additive B into the battery powder obtained after physical separation, uniformly mixing, and roasting in a nitrogen protective atmosphere, wherein the additive A is one or two of sodium sulfate and sodium chloride, and the additive B is one or two of simple substance carbon and simple substance sulfur;
s500: adding the roasted battery powder into water, continuously stirring under the protection of nitrogen, slowly adding 98% concentrated sulfuric acid, and adjusting the pH value of the solution to be 0.5-2.5, wherein the mass ratio of the battery powder to the water is 1: 2.5-10;
s600: filtering under nitrogen protection atmosphere, introducing air or oxygen into the filtered solution, stirring for 2-10 hr, and filtering to obtain H2TiO3Precipitating and dissolving nickel, cobalt, manganese and lithium sulfate;
s700: adding water and an impurity removing agent into the nickel-cobalt-manganese-lithium sulfate solution, adjusting the pH value of the nickel-cobalt-manganese-lithium sulfate solution to 3.5-5.0, and filtering to obtain the nickel-cobalt-manganese-lithium sulfate solution with impurities removed;
s800: adding an ion concentration regulator into the nickel-cobalt-manganese-lithium sulfate solution after the impurities are removed to enable the molar ratio of nickel, cobalt and manganese in the nickel-cobalt-manganese-lithium sulfate solution after the impurities are removed to be one of 1:1:1, 5:2:3, 6:2:2 or 8:1:1, then adding a sodium hydroxide solution, filtering, washing and drying to obtain a nickel-cobalt-manganese three-element composite hydroxide, filtering to obtain a lithium solution, and performing sodium carbonate precipitation, filtering, washing and drying to obtain lithium carbonate.
Example 1
Step 1: crushing the pretreated waste nickel cobalt lithium manganate-lithium titanate battery to obtain a crushed material;
step 2: placing the crushed materials in a closed environment for heating reaction, collecting condensed electrolyte through negative pressure to obtain solid materials, wherein the reaction temperature is 150 ℃, and the collected electrolyte can be reused as the electrolyte of a battery through purification;
and step 3: carrying out physical separation on the solid material to obtain copper, iron, aluminum, a diaphragm and battery powder, wherein the content of copper in the battery powder is 0.2-6.0%, the content of aluminum is 0.2-6.0%, and the content of iron is 0.2-6.0%;
and 4, step 4: adding sodium sulfate and simple substance carbon into the battery powder obtained after the physical separation, uniformly mixing, and roasting in a nitrogen protective atmosphere;
and 5: adding the roasted battery powder into water, continuously stirring under the protection of nitrogen, slowly adding 98% concentrated sulfuric acid, and adjusting the pH value of the solution to be 1.0, wherein the mass ratio of the battery powder to the water is 1: 5;
step 6: filtering under nitrogen atmosphereIntroducing air or oxygen into the solution, stirring for 5 hr, and filtering to obtain H2TiO3Precipitating and dissolving nickel, cobalt, manganese and lithium sulfate;
and 7: adding water, cobalt hydroxide, cobalt carbonate and manganese hydroxide into the nickel-cobalt-manganese-lithium sulfate solution, adjusting the pH value of the nickel-cobalt-manganese-lithium sulfate solution to 4.0, and filtering to obtain the nickel-cobalt-manganese-lithium sulfate solution with impurities removed;
and 8: adding nickel sulfate and nickel chloride into the nickel-cobalt-manganese-lithium sulfate solution after the impurities are removed to enable the molar ratio of nickel, cobalt and manganese in the nickel-cobalt-manganese-lithium sulfate solution after the impurities are removed to be 5:2:3, then adding a sodium hydroxide solution, filtering, washing and drying to obtain a nickel-cobalt-manganese three-element composite hydroxide, filtering to obtain a lithium solution, and performing sodium carbonate precipitation, filtering, washing and drying to obtain lithium carbonate. Wherein, the nickel-cobalt-manganese three-element composite hydroxide can reach GB/T26300-2020 nickel-cobalt-manganese three-element composite hydroxide national standard, and the lithium carbonate can reach YST 582-.
Example 2
Step 1: firstly, discharging waste nickel cobalt lithium manganate-lithium titanate batteries, and crushing to obtain a crushed material;
step 2: placing the crushed materials in a closed environment for heating reaction, collecting condensed electrolyte through negative pressure to obtain solid materials, wherein the reaction temperature is 250 ℃, and the collected electrolyte can be reused as the electrolyte of a battery through purification;
and step 3: carrying out secondary crushing on the solid material, wherein the diameter of the material after secondary crushing is less than 1.5 cm; screening the materials after secondary crushing, and then carrying out magnetic separation and gravity separation to obtain copper, iron, aluminum, a diaphragm and battery powder, wherein the content of copper in the battery powder is 0.2-6.0%, the content of aluminum in the battery powder is 0.2-6.0%, and the content of iron in the battery powder is 0.2-6.0%;
and 4, step 4: adding sodium chloride and elemental sulfur into the battery powder obtained after physical separation, uniformly mixing, and roasting in a nitrogen protective atmosphere, wherein the molar ratio of lithium in the battery powder to sodium in the additive A is 1:1, and the molar ratio of lithium in the battery powder to the additive B is 1: 1;
and 5: adding the roasted battery powder into water, continuously stirring under the protection of nitrogen, slowly adding 98% concentrated sulfuric acid, and adjusting the pH value of the solution to be 2.5, wherein the mass ratio of the battery powder to the water is 1: 10;
step 6: filtering under the condition of nitrogen protection atmosphere, dissolving out lithium, titanium and nickel cobalt manganese, filtering to obtain residue containing acetylene black, copper, iron and aluminum, filtering to obtain solution, introducing air or oxygen, stirring for 10 hr, and filtering to obtain H2TiO3Precipitating and dissolving nickel, cobalt, manganese and lithium sulfate;
and 7: adding water, sodium hydroxide, sodium carbonate, nickel hydroxide, nickel carbonate and cobalt hydroxide into the nickel-cobalt-manganese-lithium sulfate solution, adjusting the pH value of the nickel-cobalt-manganese-lithium sulfate solution to 5.0, filtering to obtain the nickel-cobalt-manganese-lithium sulfate solution with impurities removed, wherein the ion concentration range in the nickel-cobalt-manganese-lithium sulfate solution with impurities removed meets the following requirements: ni + Co + Mn + Li is more than or equal to 60g/L and less than or equal to 160g/L, and the mass ratio of ions meets the following requirements: (Ni + Co + Mn + Li)/(Cu + Fe + Al + Ca + Mg) is not less than 3300;
and 8: adding manganese sulfate and manganese chloride into the nickel-cobalt-manganese-lithium sulfate solution after the impurities are removed to enable the molar ratio of nickel, cobalt and manganese in the nickel-cobalt-manganese-lithium sulfate solution after the impurities are removed to be 8:1:1, then adding a sodium hydroxide solution, filtering, washing and drying to obtain a nickel-cobalt-manganese three-element composite hydroxide, filtering to obtain a lithium solution, and carrying out sodium carbonate precipitation, filtering, washing and drying to obtain lithium carbonate. Wherein, the nickel-cobalt-manganese three-element composite hydroxide can reach GB/T26300-2020 nickel-cobalt-manganese three-element composite hydroxide national standard, and the lithium carbonate can reach YST 582-.
Example 3
Step 1: firstly, discharging waste nickel cobalt lithium manganate-lithium titanate batteries, and crushing to obtain a crushed material;
step 2: placing the crushed materials in a closed environment for heating reaction, collecting condensed electrolyte through negative pressure to obtain solid materials, wherein the reaction temperature is 100 ℃, and the collected electrolyte can be reused as the electrolyte of a battery through purification;
and step 3: carrying out physical separation on the solid material to obtain copper, iron, aluminum, a diaphragm and battery powder, wherein the content of copper in the battery powder is 0.2-6.0%, the content of aluminum is 0.2-6.0%, and the content of iron is 0.2-6.0%;
and 4, step 4: adding sodium sulfate, sodium chloride, simple substance carbon and simple substance sulfur into the battery powder obtained after physical separation, uniformly mixing, and roasting in a nitrogen protective atmosphere, wherein the molar ratio of lithium in the battery powder to sodium in the additive A is 1:5, and the molar ratio of lithium in the battery powder to the additive B is 1: 2;
and 5: adding the roasted battery powder into water, continuously stirring under the protection of nitrogen, slowly adding 98% concentrated sulfuric acid, and adjusting the pH value of the solution to be 0.5, wherein the mass ratio of the battery powder to the water is 1: 2.5;
step 6: filtering under the condition of nitrogen protection atmosphere, dissolving out lithium, titanium and nickel cobalt manganese, filtering to obtain residue containing acetylene black, copper, iron and aluminum, filtering to obtain solution, introducing air or oxygen, stirring for 2 hr, and filtering to obtain H2TiO3Precipitating and dissolving nickel, cobalt, manganese and lithium sulfate;
and 7: adding water and lithium sulfide into the nickel-cobalt-manganese-lithium sulfate solution, adjusting the pH value of the nickel-cobalt-manganese-lithium sulfate solution to 3.5, filtering to obtain the nickel-cobalt-manganese-lithium sulfate solution with impurities removed, wherein the ion concentration range in the nickel-cobalt-manganese-lithium sulfate solution with impurities removed meets the following requirements: ni + Co + Mn + Li is more than or equal to 60g/L and less than or equal to 160g/L, and the mass ratio of ions meets the following requirements: (Ni + Co + Mn + Li)/(Cu + Fe + Al + Ca + Mg) is not less than 3300;
and 8: adding manganese sulfate and manganese chloride into the nickel-cobalt-manganese-lithium sulfate solution after the impurities are removed to enable the molar ratio of nickel, cobalt and manganese in the nickel-cobalt-manganese-lithium sulfate solution after the impurities are removed to be 1:1:1, then adding a sodium hydroxide solution, filtering, washing and drying to obtain a nickel-cobalt-manganese three-element composite hydroxide, filtering to obtain a lithium solution, and carrying out sodium carbonate precipitation, filtering, washing and drying to obtain lithium carbonate. Wherein, the nickel-cobalt-manganese three-element composite hydroxide can reach GB/T26300-2020 nickel-cobalt-manganese three-element composite hydroxide national standard, and the lithium carbonate can reach YST 582-.
Example 4
Step 1: firstly, discharging waste nickel cobalt lithium manganate-lithium titanate batteries, and crushing to obtain a crushed material;
step 2: placing the crushed materials in a closed environment for heating reaction, collecting condensed electrolyte through negative pressure to obtain solid materials, wherein the reaction temperature is 200 ℃, and the collected electrolyte can be reused as the electrolyte of a battery through purification;
and step 3: carrying out physical separation on the solid material to obtain copper, iron, aluminum, a diaphragm and battery powder, wherein the content of copper in the battery powder is 0.2-6.0%, the content of aluminum is 0.2-6.0%, and the content of iron is 0.2-6.0%;
and 4, step 4: adding sodium sulfate, simple substance carbon and simple substance sulfur into the battery powder obtained after physical separation, uniformly mixing, and roasting in a nitrogen protective atmosphere, wherein the molar ratio of lithium in the battery powder to sodium in the additive A is 1:10, and the molar ratio of lithium in the battery powder to the additive B is 1: 3.5;
and 5: adding the roasted battery powder into water, continuously stirring under the protection of nitrogen, slowly adding 98% concentrated sulfuric acid, and adjusting the pH value of the solution to be 2.0, wherein the mass ratio of the battery powder to the water is 1: 8;
step 6: filtering under the condition of nitrogen protection atmosphere, dissolving out lithium, titanium and nickel cobalt manganese, wherein acetylene black, copper, iron and aluminum are contained in filter residues, introducing air or oxygen into the solution obtained after filtering dissolved matters, continuously stirring for 8H, and filtering to obtain H2TiO3Precipitating and dissolving nickel, cobalt, manganese and lithium sulfate;
and 7: adding water and lithium sulfide into the nickel-cobalt-manganese-lithium sulfate solution, adjusting the pH value of the nickel-cobalt-manganese-lithium sulfate solution to 4.5, filtering to obtain the nickel-cobalt-manganese-lithium sulfate solution with impurities removed, wherein the ion concentration range in the nickel-cobalt-manganese-lithium sulfate solution with impurities removed meets the following requirements: ni + Co + Mn + Li is more than or equal to 60g/L and less than or equal to 160g/L, and the mass ratio of ions meets the following requirements: (Ni + Co + Mn + Li)/(Cu + Fe + Al + Ca + Mg) is not less than 3300;
and 8: adding manganese sulfate and manganese chloride into the nickel-cobalt-manganese-lithium sulfate solution after the impurities are removed to enable the molar ratio of nickel, cobalt and manganese in the nickel-cobalt-manganese-lithium sulfate solution after the impurities are removed to be 6:2:2, then adding a sodium hydroxide solution, filtering, washing and drying to obtain a nickel-cobalt-manganese three-element composite hydroxide, filtering to obtain a lithium solution, and carrying out sodium carbonate precipitation, filtering, washing and drying to obtain lithium carbonate. Wherein, the nickel-cobalt-manganese three-element composite hydroxide can reach GB/T26300-2020 nickel-cobalt-manganese three-element composite hydroxide national standard, and the lithium carbonate can reach YST 582-.
In order to make those skilled in the art better understand the technical solutions in the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making creative efforts based on the embodiments of the present invention, shall fall within the protection scope of the present invention.
Claims (8)
1. A method for recycling waste nickel cobalt lithium manganate-lithium titanate batteries is characterized by comprising the following steps:
step 1: crushing the pretreated waste nickel cobalt lithium manganate-lithium titanate battery to obtain a crushed material;
step 2: placing the crushed materials in a closed environment for heating reaction, and collecting condensed electrolyte through negative pressure to obtain solid materials, wherein the reaction temperature is 100-250 ℃;
and step 3: carrying out physical separation on the solid material to obtain copper, iron, aluminum, a diaphragm and battery powder;
and 4, step 4: adding an additive A and an additive B into the battery powder obtained after physical separation, uniformly mixing, and roasting in a nitrogen protective atmosphere, wherein the additive A is one or two of sodium sulfate and sodium chloride, and the additive B is one or two of simple substance carbon and simple substance sulfur;
and 5: adding the roasted battery powder into water, continuously stirring under the protection of nitrogen, slowly adding 98% concentrated sulfuric acid, and adjusting the pH value of the solution to be 0.5-2.5, wherein the mass ratio of the battery powder to the water is 1: 2.5-10;
step 6: filtering under nitrogen protection atmosphere, introducing air or oxygen into the filtered solution, stirring for 2-10 hr, and filtering to obtain H2TiO3Precipitating and dissolving nickel, cobalt, manganese and lithium sulfate;
and 7: adding water and an impurity removing agent into the nickel-cobalt-manganese-lithium sulfate solution, adjusting the pH value of the nickel-cobalt-manganese-lithium sulfate solution to 3.5-5.0, and filtering to obtain the nickel-cobalt-manganese-lithium sulfate solution with impurities removed;
and 8: adding an ion concentration regulator into the nickel-cobalt-manganese-lithium sulfate solution after the impurities are removed to enable the molar ratio of nickel, cobalt and manganese in the nickel-cobalt-manganese-lithium sulfate solution after the impurities are removed to be one of 1:1:1, 5:2:3, 6:2:2 or 8:1:1, then adding a sodium hydroxide solution, filtering, washing and drying to obtain a nickel-cobalt-manganese three-element composite hydroxide, filtering to obtain a lithium solution, and performing sodium carbonate precipitation, filtering, washing and drying to obtain lithium carbonate.
2. The method of claim 1, wherein the step 3 further comprises the steps of:
carrying out secondary crushing on the solid material, wherein the diameter of the material after secondary crushing is less than 1.5 cm;
and screening the materials subjected to secondary crushing, and then carrying out magnetic separation and gravity separation to obtain copper, iron, aluminum, a diaphragm and battery powder.
3. The method as claimed in claim 1, wherein the heating temperature in step 2 is 150 ℃ to 200 ℃.
4. The method according to claim 1, wherein the impurity removing agent is one or more of sodium hydroxide, sodium carbonate, nickel hydroxide, nickel carbonate, cobalt hydroxide, cobalt carbonate, manganese hydroxide, manganese carbonate, lithium hydroxide, lithium carbonate, sodium sulfide, nickel sulfide, cobalt sulfide, manganese sulfide and lithium sulfide.
5. The method according to claim 1, wherein the ionic concentration regulator is one or more of nickel sulfate, nickel chloride, cobalt sulfate, cobalt chloride, manganese sulfate and manganese chloride.
6. The method according to claim 1, wherein the ion concentration range in the dedoped lithium nickel cobalt manganese sulfate solution in the step 7 is as follows: ni + Co + Mn + Li is more than or equal to 60g/L and less than or equal to 160g/L, and the mass ratio of ions meets the following requirements: (Ni + Co + Mn + Li)/(Cu + Fe + Al + Ca + Mg) is not less than 3300.
7. The method according to claim 1, wherein the molar ratio of lithium in the battery powder to sodium in the additive A in the step 4 is 1: 1-10, and the molar ratio of lithium in the battery powder to the additive B is 1: 1-3.5.
8. The method of claim 1, wherein the battery powder in step 3 has a copper content of 0.2% to 6.0%, an aluminum content of 0.2% to 6.0%, and an iron content of 0.2% to 6.0%.
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| CN115584397A (en) * | 2022-11-24 | 2023-01-10 | 中自环保科技股份有限公司 | Method for recovering lithium, lanthanum, zirconium, titanium and oxygen in lithium ion semi-solid battery |
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| CN115584397A (en) * | 2022-11-24 | 2023-01-10 | 中自环保科技股份有限公司 | Method for recovering lithium, lanthanum, zirconium, titanium and oxygen in lithium ion semi-solid battery |
| CN115584397B (en) * | 2022-11-24 | 2023-03-24 | 中自环保科技股份有限公司 | Method for recovering lithium, lanthanum, zirconium, titanium and oxygen in lithium ion semi-solid battery |
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Address after: No.1 circular Avenue, Dashi circular economy industrial park, Dongwan village, shuidongjiang office, Leiyang City, Hengyang City, Hunan Province Patentee after: Hunan Jinkai Recycling Technology Co.,Ltd. Address before: No.1 circular Avenue, Dashi circular economy industrial park, Dongwan village, shuidongjiang office, Leiyang City, Hengyang City, Hunan Province Patentee before: HUNAN KEYKING CYCLE TECHNOLOGY Co.,Ltd. |
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